US6462132B2 - Thermoplastic elastomer composition and molded articles made thereof - Google Patents

Thermoplastic elastomer composition and molded articles made thereof Download PDF

Info

Publication number
US6462132B2
US6462132B2 US09/756,290 US75629001A US6462132B2 US 6462132 B2 US6462132 B2 US 6462132B2 US 75629001 A US75629001 A US 75629001A US 6462132 B2 US6462132 B2 US 6462132B2
Authority
US
United States
Prior art keywords
thermoplastic elastomer
elastomer composition
composition according
parts
thermoplastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09/756,290
Other versions
US20020132920A1 (en
Inventor
Edwin Willems
Mohammad R. Sadeghi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DSM IP Assets BV
Original Assignee
DSM NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM NV filed Critical DSM NV
Priority to US09/756,290 priority Critical patent/US6462132B2/en
Assigned to DSM N.V. reassignment DSM N.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SADEGHI, MOHAMMAD REZA, WILLEMS, EDWIN
Priority to DE60201254T priority patent/DE60201254T2/en
Priority to AU2002228445A priority patent/AU2002228445A1/en
Priority to EP02710524A priority patent/EP1349891B1/en
Priority to PCT/NL2002/000006 priority patent/WO2002055599A2/en
Priority to JP2002556659A priority patent/JP2004522832A/en
Priority to AT02710524T priority patent/ATE276310T1/en
Priority to US10/451,812 priority patent/US20040097649A1/en
Publication of US20020132920A1 publication Critical patent/US20020132920A1/en
Publication of US6462132B2 publication Critical patent/US6462132B2/en
Application granted granted Critical
Assigned to DSM IP ASSETS B.V. reassignment DSM IP ASSETS B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DSM N.V.
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0884—Epoxide containing esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The subject invention relates to a thermoplastic elastomer composition that contains a dynamically vulcanized thermoplastic elastomer (a) on the basis of a thermoplastic polyolefin and an at least partly dynamically vulcanized rubber, a thermoplastic polyester block copolymer (b) and a compatibilizer (c). The thermoplastic polyolefin is preferably a propylene homo- or copolymer. The rubber is preferably an EPDM or EPM copolymer. The thermoplastic polyester block copolymer is preferably a polyether ester block copolymer. The thermoplastic elastomer composition according to the invention for instance contains 20-80 parts (a), 80-20 parts (b), and 1-40 parts (c), the sum of the parts (a+b+c) being 100. The thermoplastic elastomer composition according to the invention also relates to molded articles that contains the thermoplastic elastomer composition.

Description

The invention relates to a thermoplastic elastomer composition and molded parts thereof.
A thermoplastic elastomer composition is known inter alia from Polymer Blends, Volume 2: Performance, edited by D. R. Paul and C. B. Sucknall, ISBN 0-471-36280-2, 2000. This article describes thermoplastic elastomers on the basis of a thermoplastic polymer and a dynamically vulcanized rubber which is dispersed in a continuous phase of the thermoplastic polymer in the form of fine particles. Such thermoplastic elastomers, thermoplastic vulcanisates, hereinafter called (TPV's), possess a number of properties of an elastomer and can be processed among other things as a thermoplastic polymer
The most widely used TPV's have a polyolefin as thermoplastic polymer. As a consequence, these TPV's adhere only to apolar substrates and they do not adhere, or only with difficulty, to polar substrates. To improve the adhesion, the substrate is often pretreated. Industrially used pretreatment methods are dependent on the substrate and may for instance be chromic acid etching. ozone treatment, UV irradiation, primer coatings or plasma treatment. However, these pretreatments are expensive, use hazardous substances, result in product degradation and involve environmental risks.
The aim of the present invention is to provide a thermoplastic elastomer composition that exhibits intrinsically good adhesion to polar and apolar substrates while it does not have the above-mentioned disadvantages.
This aim is achieved according to the invention with a thermoplastic elastomer composition that contains a blend of:
a. a dynamically vulcanized thermoplastic elastomer containing a thermoplastic polyolefin and an at least partly dynamically vulcanized rubber
b. a thermoplastic polyester block copolymer
c. a compatibilizer.
It has, surprisingly, been found that the thermoplastic elastomer composition according to the invention exhibits particular good adhesion to apolar but in particular also to polar substrates, it being possible to leave out the pretreatment of the substrate.
A further advantage is that a thermoplastic elastomer composition is obtained with a relatively low hardness and good mechanical properties.
Examples of suitable thermoplastic polyolefins used in the thermoplastic elastomer composition according to the invention are thermoplastic semi-crystalline polyolefin homo- and copolymers or blends thereof. Examples of these are homopolymers of ethylene or propylene, copolymers of ethylene and propylene, copolymers of ethylene and an alpha-olefin with 4-12 carbon atoms or copolymers of propylene and an alpha-olefin with 4-12 carbon atoms, It is essential that the ethylene or propylene content in the copolymers is so high that the copolymer is semi-crystalline. In the case of statistic copolymers this is usually achieved at an ethylene or propylene content of about 70 mol % or more. Preferably, a homopolymer of propylene is used.
Examples of rubbers that can be used in the thermoplastic elastomer composition according to the invention are rubbers that are suitable for dynamic vulcanization. Examples of such rubbers are ethylene-propylene copolymers, hereinafter called EPM, ethylenlpropylene-dione terpolymers, hereinafter called EPDM, styrene butadiene rubber, nitrile butadiene rubber, isobutene-isoprene rubber, styrene-ethylene/styrene-butadiene block copolymers, butyl rubber, isobutylene-p-methylstyrene copolymers or brominated Isobutylene-p-methylstyrene copolymers. natural rubber or blends of these. Preferably, EPDM or EPM is used as rubber. Mast preferably, EPDM is used as rubber. The EPDM preferably contains 50-70 parts by weight ethylene monomer units, 48-30 parts by weight monomer units originating from an alpha-olefin and 2-12 parts by weight monomer units originating from a non-conjugated diene. As alpha-olefin use is preferably made of propylene. As non-conjugated diene use is preferably made of dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene (ENB) or vinylnorbornene (VNB).
The dynamic vulcanization of the rubber is carried out in the presence of a suitable vulcanization agent such as, for instance, sulfur, sulfurous compounds, metal oxides, maleimides, phenol resins or peroxides. These vulcanization systems are known from the state of the art and are described in U.S. Pat. No. 5,100,947, It is also possible to use siloxane compounds as vulcanization agent, examples are hydrositane or vinylalkoxysilane. The thermoplastic elastomer composition according to the invention is preferably vulcanized with the aid of phenol resins, siloxanes or peroxides as vulcanization agent. The degree of vulcanization can be expressed in terms of gel content This method is described in U.S. Pat. No. 5,100,947.
The rubber in the thermoplastic elastomer composition according to the invention is at least partly vulcanized and for instance has a gel content between 60 and 100%. More preferably, the rubber has a gel content between 80 and 100%. Most preferably, the rubber is fully vulcanized and has a gel content in excess of 95%.
The polyester block copolymer used in the thermoplastic elastomer composition according to the invention preferably consists of soft blocks of a flexible polymer segment and hard blocks of a non flexible polymer segment.
The soft blocks of the flexible polymer segments for instance have a molecular mass of 400-6000 g/mol; preferably they have a molecular mass of 500-3000 g/mol. Examples of soft blocks are aliphatic polyether segments or aliphatic polyester segments. Examples of aliphatic polyester segments are polybutylene adipate segments or polycaprolactone segments. Examples of aliphatic polyether segments are polyalkylene-oxide glycol segments such as for instance polyethylene-oxide glycol segments, polypropylene-oxide glycol segment, polytetramethylene-oxide glycol segments or ethylene oxide-terminated polypropylene-oxide glycol segments.
Preferably, an aliphatic polyether segment is used as soft block in the polyester block copolymer. More preferably, ethylene oxide-terminated polypropyleneoxide glycol segments or polytetramethylene-oxide glycol segments are used.
The hard blocks in the polyester block copolymer preferably consist of repeating units of at least one alkylene glycol and at least one aromatic clicarboxylic acid or an ester thereof. The alkylene group generally contains 2-6 carbon atoms, preferably 2-4 carbon atoms. Examples are ethylene glycol, propylene glycol or butylene glycol. Preferably, use is made of propylene glycol or butylene glycol. More preferably, use is made of butylene glycol. Examples of aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid or 4,4′-diphenyl dicarboxylic acid. Examples of the hard polyester blocks are polyethylene terephthalate segments, polypropylene terephthalate segments or polybutylene terephthalate segments. Preferably, polybutylene terephthalate segments are used as hard polyester block.
The ratio between the soft and hard blocks in the polyester block copolymer can generally vary within wide limits, but is chosen in particular in light of the desired hardness of the polyester block copolymer. The hardness may generally vary between 20 and 80 Shore D.
Most preferably. the polyester block copolymer is a block copolymer with hard blocks derived from polybutylene terephthalate segments and soft blocks derived from polytetramethylene-oxide glycol segments or ethylene oxide-terminated polypropylene-oxide glycol segments.
The polyester block copolymer may further contain the customary additives such as stabilizers, colorants, processing aids or flame-retarding compounds. Examples and the preparation of polyester block copolymers are described inter alia in Handbook of Thermoplastics, ed. O. Olabishi, Chapter 17, Marcel Dekker Inc., New York 1997, ISBN 0-8247-9797-3. in Thermoplastic Elastomers, 2nd Ed, Chapter 8, Carl Hanser Verlag (1996) ISBN 1-56990-205-4, and in Encyclopedia of Polymer Science and Engineering, Vol. 12, Wiley & Sons, New York (1988), ISBN 0-471-80944. pp. 75-117 and the references given there
The compatibilizer (c) in the thermoplastic elastomer composition according to the invention is compatible with both the dynamically vulcanized thermoplastic elastomer (a) and the thermoplastic polyester block copolymer (b).
Compatibilizers that can be used in the thermoplastic elastomer composition according to the invention are functionalized polymers such as for instance epoxy or acid functionalized polymers. Preferably the epoxy or acid functionalized polymers are epoxy or acid functionalized olefine polymers. Examples of epoxy functionalized olefine polymers are copolymers of ethylene-glyciclyl methacrylate or ethylene-glycidyl scrylate or terpolymers of ethylene-glycidyl methacrylate acrylate or glycidyl methacrylate functionalized polyethylene or glycidyl methacylate functionalized acrylate terpolymers. Examples of acid functionalized olefine polymers are maleic anhydride functionalized olefine polymers such as maleic anhydride functionalized polypropylene or maleic anhydride functionalized polyethylene. Preferably, an epoxy functionalized olefin polymer is used as compatibilizer in the thermoplastic composition according to the invention.
The thermoplastic elastomer composition according to the invention for instance contains 20-80 parts (a), 80-20 parts (b) and 1-40 parts (c) the sum of the parts (a+b+c) being 100.
Preferably, the thermoplastic elastomer composition according to the invention contains 30-70 parts (a), 70-30 parts (b) and 5-20 parts (c), the sum of the parts of (a+b+c) being 100.
The thermoplastic elastomer composition according to the invention optionally contains other customary additives. Examples of such additives are reinforcing and non-reinforcing fillers, plasticizers, antioxidants, stabilizers, oil, antistatic agents, waxes, foaming agents, pigments, flame retardants and other known agents and are described in the Rubber World Magazine Blue Book, and in Gaether et al., Plastics Additives Handbook, (Hanser 1990). Examples of fillers that can be used are calcium carbonate, clay, silica, talc, titanium dioxide, and carbon. Examples of oil that can be added are paraffinic oil, naphthenic oil or aromatic oil obtained from petroleum fractions. Another additive that can optionally be added to the thermoplastic composition according to the invention is a Lewis base such as for instance a metal oxide, a metal hydroxide, a metal carbonate or hydrotaicite.
The additives can be added during the preparation of the TPV or during the preparation of the thermoplastic elastomer composition according to the invention or during both. The quantity of additive to be added is known to one skilled in the art.
The thermoplastic elastomer composition can be prepared via two successive steps but can also be prepared In one step. If the thermoplastic elastomer composition is prepared in two successive steps, in a first step the TPV will be prepared by blending the thermoplastic olefinic polymer, the rubber and other additives customarily employed by one skilled in the art in for instance a Brabender blender. After these components have been properly dispersed, the vulcanization agent is added to initiate the dynamic vulcanization. This blend results in a TPV. In a second step the TPV is introduced into an extruder and blended with the polyester block copolymer and the compatibilizer. These two steps can be carried out independently as separate steps or sequentially in the same equipment. It is also possible for the thermoplastic elastomer composition according to the invention to be prepared in a single step, with the TPV, the polyester block copolymer and the compatibilizer being introduced simultaneously into the extruder and be blended further with the additives customarily employed by one skilled in the art. It is also possible to prepare a TPV in a first step, which Is subsequently blended with a compatibilizer in the same extruder. Next, the resulting TPV masterbatch can be blended with the polyester block copolymer.
The thermoplastic elastomer composition according to the invention can for instance be blended with one or more polymers chosen from styrene-butadiene-styrene rubber (SBS), styrene-ethylene/styrene-butadiene block copolymers (SEES). styrene-propylene-styrene terpolymers (SPS), styrenes isopropylene-styrene terpolymers (SIPS), polyvinyl chloride, polycarbonate, acrylonitrile-butadienestyrene terpolymers, polybutylene terephthalate, polypropylene, styrene-acrylonitrile copolymers, styrenemalsic anhydride copolymers, polyphenylene oxide, or polyethylene. This for instance involves adding 1-40 parts of the above-mentioned polymers relative to the parts of the total composition (a+b+c). Preferably, 1-20 parts of the above-mentioned polymers are added relative to the parts of the total composition (a+b+c).
The invention also relates to molded articles that contain the thermoplastic elastomer composition according to the invention. The invention particularly relates to moulded articles comprising a substrate part and a part that comprises the thermoplastic elastomer according to the invention whereby the parts are being adhered. It has been found that the thermoplastic elastomer composition according to the invention exhibits particularly good adhesion to both polar and apolar substrates. Preferably, the adhesion between the thermoplastic elastomer composition according to the invention and the substrate is such that cohesive failure takes place, both when the substrate is polar and when it is apolar. Cohesive failure takes place when the adhesion between the thermoplastic elastomer composition according to the invention and the substrate is stronger than the thermoplastic elastomer composition.
The molded articles can be prepared using processing methods customarily employed by one skilled in the art, examples being co-extrusion, blow molding of two or more components. injection molding of two or more components, robotic extrusion, or injection overmolding.
The thermoplastic elastomer composition according to the invention can for instance be used in door profiles, wire & cables, hoses, dashboard films, window encapsulation and soft touch grips.
The invention will be elucidated with reference to the following examples, without being limited thereto.
The materials used In the examples are the following:
Arnitel™ DM400 (38 Shore D copolyether aster, DSM)
Arnitel™ EM550 (55 Shore D copolyether ester, DSM)
Arnitel™ EM630 (63 Shore D copolyether ester, DSM)
TPV40 (40 Shore A PP-EPDM-oil TPV)
Lotader™ AX8840 (GMA functionalized PE, Elf Atochem)
Lotader™ AX8860 (terpolymer of ethylene, acrylic ester and glycidyl methacrylate
(GMA), Elf Atochem)
Lotader™ AX8930 (GMA functionalized acrylate terpolymer, Elf Atochem)
The measurements in the examples were carried out using the following tests:
Hardness DIN 53505
Mechanical properties ISO 37
Compression set ISO 815
EXAMPLE 1
TPV40 is produced by melt blending 45% EPDM, 10% PP, 35% paraffinic oil, 0.5% phenolic resin, 0.5% stannous chloride and 0.5% stabilizer on a 40 mm co-rotating twin screw extruder at a melt temperature of 250° C.
In a second step the thermoplastic elastomer composition is produced by melt blending the TPV40 with a copolyether ester (Arnitel™ EM400) and an epoxy functionalized compatibilizer (Lotader™ 8860) on a 30 mm co-rotating twin screw extruder at a melt temperature of 230° C.
The adhesion properties are tested by co-extruding 1 mm strip of the thermoplastic elastomer composition on top of different substrates (2 mm of polycarbonate, ABS and polypropylene) at a temperature of 220° C. The adhesion after co-extrusion is evaluated by ranking the peel strength and is classified as either no, poor or strong adhesion and the type of failure is classified as either adhesive or cohesive.
The mechanical properties and adhesion results are shown in table 1.
COMPARATIVE EXAMPLE A
The same procedure as in example 1 is followed but instead of an epoxy functionalized compatibilizer no compatibilizer is used. The mechanical properties and adhesion results are shown in table 1.
COMPARATIVE EXAMPLE B
The same procedure as in example 1 is followed but no copolyether ester is added. The mechanical properties and adhesion results are shown in table 1.
COMPARATIVE EXAMPLE C
The same procedure as in example 1 is followed but no TPV-40 is added.
The mechanical properties and adhesion results are shown in table 1.
TABLE 1
A B C 1
Composition
Arnitel ™ EM400 50% 90% 50%
TPV-40 50% 90% 40%
Lotader ™ AX8860 10% 10% 10%
Mechanical properties
Hardness [Shore A] 75 41 96 75
Tensile strength [Mpa] 1.3 3.9 14.1 6.5
Elongation [%] 95 310 510 330
Adhesion onto PC Poor No Strong Strong
Type of failure Adhesive Adhesive Cohesive Cohesive
Adhesion onto ABS Poor No Strong Strong
Type of failure Adhesive Adhesive Cohesive Cohesive
Adhesion onto PP Poor Strong No Strong
Type of failure Adhesive Cohesive Adhesive Cohesive
From table 1 it is clear that in comparative examples A, B and C there is no or poor adhesion to polar and apolar substrates. The type of failure is in most cases adhesive instead of cohesive. In example 1 very good adhesion to polar and apolar substrates was found, while the type of failure was cohesive in every case.
EXAMPLES 2 to 6
TPV40 is produced by melt blending 45% EPOM, 10% PP, 35% paraffinic oil, 0.5% phenolic resin, 0.5% stannous chloride and 0.5% stabilizer on a 40 mm co-rotating twin screw extruder at a melt temperature of 250° C. In the same extrusion step the copolyether ester (Arnitel™ EM400) and an epoxy functionalized compatibilizer (Lotader™ AX8930) are added in different concentrations.
The adhesion properties are tested by injection molding 30×30×2 mm plaques of the thermoplastic elastomer composition against the small side of 30×30×2 mm plaques of different substrates (polycarbonate, ABS and polypropylene) at a temperature of 240° C. The final part is 60×60×2 mm. The adhesion after injection molding is evaluated by cutting test bars across the interface and measuring the mechanical strength of the 2K test bar. Besides the adhesion strength, the type of failure is classified as either adhesive or cohesive.
The mechanical and adhesion properties are shown in table 2.
TABLE 2
2 3 4 5 6
Composition
Arnitel ™ EM400 60 50 40 30 20
TPV-40 25 35 45 50 60
Lotader ™ AX8930 15 15 15 20 20
Mechanical properties
Hardness [Shore A] 80 75 68 63 55
Tensile strength [Mpa] 7.9 6.7 5.0 4.7 4.0
Elongation [%] 490 375 280 200 180
C. set 72h/23° C. [%] 29 30 30 31 31
C. set 22h/70° C. [%] 46 48 51 48 45
Adhesion to PC [Mpa] 5.9 5.0 3.7 3.4 2.9
Type of failure Cohesive Cohesive Cohesive Cohesive Cohesive
Adhesion to ABS [Mpa] 5.1 4.3 3.1 2.8 2.1
Type of failure Cohesive Cohesive Cohesive Cohesive Cohesive
Adhesion to PP [Mpa] 5.6 4.9 3.8 3.7 3.1
Type of failure Cohesive Cohesive Cohesive Cohesive Cohesive
Table 2 shows that the use of a larger amount of Arnitel™ EM400 in the thermoplastic elastomer composition according to the invention results in stronger adhesion to both the polar and the apolar substrates. In all the type of failure is cohesive.
EXAMPLES 7 to 9
TPV40 is produced by melt blending 45% EPDM, 10% PP, 35% paraffinic oil. 0.5% phenolic resin, 0.5% stannous chloride and 0.5% stabilizer on a 40 mm co-rotating twin screw extruder at a melt temperature of 250° C. In the same extrusion step the epoxy functionalized compatibilizer (Lotader™ AX8930) is added.
In a second step the thermoplastic elastomer composition is produced by melt blending TPV-40 (including an epoxy functionalized compatibilizer, Lotader™ AX8840) with different copolyether esters (Arnitel™ EM400, EM550, EM630) on a 30 mm co-rotating twin screw extruder at a melt temperature of 230° C.
The adhesion properties are tested by injection molding 2 mm plaques of the thermoplastic elastomer composition against 2 mm plaques of different substrates (polycarbonate, ABS, polypropylene, Arnitel™ EM 550 and polybutylene terephthalate) at a temperature of 240° C. The adhesion after injection molding is classified as no, poor or strong adhesion. In addition, the type of failure is classified as either adhesive or cohesive.
The mechanical and adhesion properties are shown in table 3.
TABLE 3
7 8 9
Composition
Arnitel ™ EM400 50
Arnitel ™ EM550 50
Arnitel ™ EM630 50
TPV-40 40 40 40
Lotader ™ AX8930 10 10 10
Mechanical properties
Hardness [Shore A] 75 86 93
Tensile strength [Mpa] 4.9 5.8 7.0
Elongation [%] 370 300 220
Adhesion to PC Strong Strong Strong
Type of failure Cohesive Cohesive Cohesive
Adhesion to ABS Strong Strong Strong
Type of failure Cohesive Cohesive Cohesive
Adhesion to PBT Strong Strong Strong
Type of failure Cohesive Cohesive Cohesive
Adhesion to Arnitel ™ EM550 Strong Strong Strong
Type of failure Cohesive Cohesive Cohesive
Adhesion to PP Strong Strong Strong
Type of failure Cohesive Cohesive Cohesive
Table 3 shows that the mechanical properties are influenced by the use of different types of Arnitel™. The adhesion properties, however, are strong for all the substrates. In all cases cohesive adhesion is obtained.

Claims (12)

What is claimed is:
1. Thermoplastic elastomer composition comprising,
a. i. a dynamically vulcanized thermoplastic elastomer containing a thermoplastic olefin homopolymer or copolymer of an olefin selected from the group consisting of ethylene and propylene and
ii. an at least partly dynamically vulcanized rubber;
b. a thermoplastic polyester block copolymer; and
c. a compatibilizer.
2. Thermoplastic elastomer composition according to claim 1, wherein the blend contains 20-80 parts (a), 80-20 parts (b) and 1-40 parts (c), the sum of parts (a+b+c) being 100.
3. Thermoplastic elastomer composition according to claim 1, wherein the blend contains 30-70 parts (a), 70-30 parts (b) and 5-20 parts (c), the sum of parts (a+b+c) being 100.
4. Thermoplastic elastomer composition according to claim 1, wherein the rubber is an EPDM or EPM copolymer.
5. Thermoplastic elastomer composition according to claim 1, wherein the at least partly dynamically vulcanized rubber has a gel content that is higher than 80%.
6. Thermoplastic elastomer composition according to claim 5, wherein the at least partly dynamically vulcanized rubber has a gel content that is higher than 95%.
7. Thermoplastic elastomer composition according to claim 1, wherein the thermoplastic polyester block copolymer is a polyether ester block copolymer.
8. Thermoplastic elastomer composition according to claim 1, wherein the compatibilizer is a functionalized polymer.
9. Thermoplastic elastomer composition according to claim 8, wherein the functionalized polymer is an epoxy or acid functionalized polymer.
10. Thermoplastic elastomer composition according to claim 9, wherein the epoxy functionalized polymer is an epoxy-functionalized olefin polymer.
11. Molded article comprising the thermoplastic elastomer composition according to any one of claims 1-3 or 4-10.
12. Molded article comprising a substrate part and a part that comprises the thermoplastic elastomer composition according to any one of claims 1-3 or 4-10 wherein the parts are adhered to each other.
US09/756,290 2001-01-09 2001-01-09 Thermoplastic elastomer composition and molded articles made thereof Expired - Fee Related US6462132B2 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US09/756,290 US6462132B2 (en) 2001-01-09 2001-01-09 Thermoplastic elastomer composition and molded articles made thereof
AT02710524T ATE276310T1 (en) 2001-01-09 2002-01-07 THERMOPLASTIC ELASTOMER COMPOSITION AND MOLDED PARTS MADE THEREFROM
AU2002228445A AU2002228445A1 (en) 2001-01-09 2002-01-07 Thermoplastic elastomer composition and molded articles made thereof
EP02710524A EP1349891B1 (en) 2001-01-09 2002-01-07 Thermoplastic elastomer composition and molded articles made thereof
PCT/NL2002/000006 WO2002055599A2 (en) 2001-01-09 2002-01-07 Thermoplastic elastomer composition and molded articles made thereof
JP2002556659A JP2004522832A (en) 2001-01-09 2002-01-07 Thermoplastic elastomer composition and molded article made therefrom
DE60201254T DE60201254T2 (en) 2001-01-09 2002-01-07 THERMOPLASTIC ELASTOMER COMPOSITION AND MOLDED PARTS MANUFACTURED THEREFROM
US10/451,812 US20040097649A1 (en) 2001-01-09 2002-01-07 Thermoplastic elastomer composition and molded articles made thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US09/756,290 US6462132B2 (en) 2001-01-09 2001-01-09 Thermoplastic elastomer composition and molded articles made thereof

Publications (2)

Publication Number Publication Date
US20020132920A1 US20020132920A1 (en) 2002-09-19
US6462132B2 true US6462132B2 (en) 2002-10-08

Family

ID=25042828

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/756,290 Expired - Fee Related US6462132B2 (en) 2001-01-09 2001-01-09 Thermoplastic elastomer composition and molded articles made thereof
US10/451,812 Abandoned US20040097649A1 (en) 2001-01-09 2002-01-07 Thermoplastic elastomer composition and molded articles made thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/451,812 Abandoned US20040097649A1 (en) 2001-01-09 2002-01-07 Thermoplastic elastomer composition and molded articles made thereof

Country Status (7)

Country Link
US (2) US6462132B2 (en)
EP (1) EP1349891B1 (en)
JP (1) JP2004522832A (en)
AT (1) ATE276310T1 (en)
AU (1) AU2002228445A1 (en)
DE (1) DE60201254T2 (en)
WO (1) WO2002055599A2 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010041772A1 (en) * 2000-01-28 2001-11-15 Tetsuo Masubuchi Thermoplastic elastomer composition
US20040097649A1 (en) * 2001-01-09 2004-05-20 Edwin Willems Thermoplastic elastomer composition and molded articles made thereof
US20050048238A1 (en) * 2001-06-22 2005-03-03 Pieter Gijsman Multi-layer moulding comprising tpv substrate and a weather-resistant surface layer
US20050118357A1 (en) * 2001-12-18 2005-06-02 Lange Ronald F. Instrument panel comprising a layer of a thermoplastic copolyester elastomer composition
US20070043172A1 (en) * 2003-09-17 2007-02-22 Ellul Maria D Thermoplastic vulcanizates and processes for making the same
US20070141373A1 (en) * 2005-12-20 2007-06-21 Sommerfeld Eugene G Segmented copolyesterether adhesive compositions
US20070166561A1 (en) * 2003-12-24 2007-07-19 Ticona Gmbh Composite bodies, method for the production thereof and use thereof
US20070264514A1 (en) * 2004-09-29 2007-11-15 Ticona Gmbh Composite Body Made From Polyacetal and Thermoplastic Vulcanised Elastomer
US20080029934A1 (en) * 1998-10-02 2008-02-07 Ticona Gmbh Composite body made from polyacetal and styrol olefin-elastomers
US20100112261A1 (en) * 2007-02-12 2010-05-06 Lambert Van Lumig Polymer composition and plastic tube made thereof
US20110213067A1 (en) * 2008-09-05 2011-09-01 Henkel Ag & Co. Kgaa Melt adhesive based on metallocene catalyzed olefin-a-olefin copolymers
US20120059097A1 (en) * 2010-09-06 2012-03-08 Industrial Technology Research Institute Starch-based thermoplastic composites
US20140024247A1 (en) * 2012-07-18 2014-01-23 Quirky, Inc. Wrappable extension cord apparatus and related methods

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2404985A (en) * 2003-08-13 2005-02-16 Miontec Inc Voltage compensated resistive touch panel
TWI356073B (en) * 2003-09-26 2012-01-11 Lubrizol Advanced Mat Inc A transparent thermoplastic blend of a cycloolefin
EP1612234B1 (en) * 2004-01-07 2009-10-14 Fa. M Inc. Process for producing resin composition and resin composition produced thereby
US7790809B2 (en) 2006-08-28 2010-09-07 Exxonmobil Chemical Patents Inc. Thermoplastic vulcanizates with advantageous adhesion to polar substrates
US8557393B2 (en) * 2006-10-31 2013-10-15 Exxonmobil Chemical Patents Inc. Adhesive thermoplastic vulcanizates
ATE451412T1 (en) 2007-10-11 2009-12-15 Borealis Tech Oy SOFT POLYPROPYLENE COMPOSITION WITH SOFT TOUCH FEEL
WO2011131624A1 (en) * 2010-04-20 2011-10-27 Dsm Ip Assets B.V. Polymer composition and a sealing body made of that composition
US20120048380A1 (en) * 2010-08-25 2012-03-01 Eastman Chemical Company Tubing and Methods of Making Tubing Comprising Copolyester Ether Elastomer Compositions
US8178647B2 (en) * 2010-08-25 2012-05-15 Eastman Chemical Company Copolyester ether elastomer compositions and methods of making copolyester ether elastomer compositions
CN103205210B (en) * 2013-03-19 2015-04-01 江苏鹿山光伏科技有限公司 High-temperature-resistant hot melt adhesive membrane for aluminum honeycomb boards, and preparation method thereof
DE102014218260A1 (en) * 2014-09-11 2016-03-17 Albis Plastic Gmbh Adhesion-modified olefinic thermoplastic elastomers, in particular TPE-V, TPE-O
US20160108215A1 (en) * 2014-10-18 2016-04-21 Edgar A Gonzalez Compositions containing ground vulcanized rubber and high melt flow polymer
FR3108911B1 (en) * 2020-04-07 2023-06-30 Arkema France Composition of polymers for waterproof-breathable films

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4154789A (en) * 1976-05-25 1979-05-15 Delacoste & Cie, S.A. Thermoplastic ball and method of manufacturing same
US5145402A (en) * 1990-06-06 1992-09-08 General Motors Corporation Electrical connector
US6066697A (en) * 1998-08-25 2000-05-23 The University Of Akron Thermoplastic compositions containing elastomers and fluorine containing thermoplastics

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8400968A (en) * 1983-03-14 1984-10-23 Goodyear Tire & Rubber COMPOSITION WITH PROPER BALANCE SUITABLE FOR MOLDING PURPOSES AND WITH HIGH IMPACT RESISTANCE; PROCESS TO PRODUCE IMPACT-RESISTANT MOLDING COMPOSITION
US5100947A (en) * 1989-05-26 1992-03-31 Advanced Elastomer Systems, L. P. Dynamically vulcanized alloys having improved stiffness/impact balance
JP2888305B2 (en) * 1989-09-13 1999-05-10 大成プラス株式会社 Thermoplastic elastomer composition with excellent heat fusion property
DE4343587A1 (en) * 1993-12-21 1995-06-22 Huels Chemische Werke Ag Thermoplastic polyester elastomers and process for their manufacture
EP0821035B1 (en) * 1996-02-09 2004-10-20 The Yokohama Rubber Co., Ltd. Thermoplastic elastomer composition, process for the preparation thereof, hose made by using the composition, and process for the production thereof
EP0875534A1 (en) * 1997-05-02 1998-11-04 Dsm N.V. Thermoplastic elastomer composition adhesion to polar materials
CN1342185A (en) * 1999-03-04 2002-03-27 陶氏化学公司 Polypropylene and polyester blends containing graft-modified polyolefin elastomer
US6462132B2 (en) * 2001-01-09 2002-10-08 Dsm N.V. Thermoplastic elastomer composition and molded articles made thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4154789A (en) * 1976-05-25 1979-05-15 Delacoste & Cie, S.A. Thermoplastic ball and method of manufacturing same
US5145402A (en) * 1990-06-06 1992-09-08 General Motors Corporation Electrical connector
US6066697A (en) * 1998-08-25 2000-05-23 The University Of Akron Thermoplastic compositions containing elastomers and fluorine containing thermoplastics

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080029934A1 (en) * 1998-10-02 2008-02-07 Ticona Gmbh Composite body made from polyacetal and styrol olefin-elastomers
US20010041772A1 (en) * 2000-01-28 2001-11-15 Tetsuo Masubuchi Thermoplastic elastomer composition
US20040097649A1 (en) * 2001-01-09 2004-05-20 Edwin Willems Thermoplastic elastomer composition and molded articles made thereof
US20050048238A1 (en) * 2001-06-22 2005-03-03 Pieter Gijsman Multi-layer moulding comprising tpv substrate and a weather-resistant surface layer
US7026028B2 (en) * 2001-06-22 2006-04-11 Dsm Ip Assets B.V. Multi-layer moulding
US20050118357A1 (en) * 2001-12-18 2005-06-02 Lange Ronald F. Instrument panel comprising a layer of a thermoplastic copolyester elastomer composition
US9296885B2 (en) * 2003-09-17 2016-03-29 Exxonmobil Chemical Patents Inc. Thermoplastic vulcanizates and processes for making the same
US20070043172A1 (en) * 2003-09-17 2007-02-22 Ellul Maria D Thermoplastic vulcanizates and processes for making the same
US7868096B2 (en) * 2003-09-17 2011-01-11 Exxonmobil Chemical Patents Inc. Thermoplastic vulcanizates and processes for making the same
US20100324161A1 (en) * 2003-09-17 2010-12-23 Maria Dolores Ellul Thermoplastic Vulcanizates and Processes for Making the Same
US20070166561A1 (en) * 2003-12-24 2007-07-19 Ticona Gmbh Composite bodies, method for the production thereof and use thereof
US20070264514A1 (en) * 2004-09-29 2007-11-15 Ticona Gmbh Composite Body Made From Polyacetal and Thermoplastic Vulcanised Elastomer
US7858202B2 (en) 2004-09-29 2010-12-28 Ticona Gmbh Composite bodies having a polyacetal portion and a thermoplastic vulcanized elastomer portion, processes for making the same, articles including such bodies and uses therefor
US20080306216A1 (en) * 2005-12-20 2008-12-11 Henkel Corporation Adhesive and coating compositions
US20070141373A1 (en) * 2005-12-20 2007-06-21 Sommerfeld Eugene G Segmented copolyesterether adhesive compositions
US20100112261A1 (en) * 2007-02-12 2010-05-06 Lambert Van Lumig Polymer composition and plastic tube made thereof
US20110213067A1 (en) * 2008-09-05 2011-09-01 Henkel Ag & Co. Kgaa Melt adhesive based on metallocene catalyzed olefin-a-olefin copolymers
US8163833B2 (en) 2008-09-05 2012-04-24 Henkel Ag & Co. Kgaa Melt adhesive based on metallocene catalyzed olefin-α-olefin copolymers
US20120059097A1 (en) * 2010-09-06 2012-03-08 Industrial Technology Research Institute Starch-based thermoplastic composites
US20140024247A1 (en) * 2012-07-18 2014-01-23 Quirky, Inc. Wrappable extension cord apparatus and related methods
US10186792B2 (en) * 2012-07-18 2019-01-22 Quirky Ip Licensing Llc Wrappable extension cord apparatus and related methods

Also Published As

Publication number Publication date
US20040097649A1 (en) 2004-05-20
AU2002228445A1 (en) 2002-07-24
WO2002055599A3 (en) 2002-10-03
ATE276310T1 (en) 2004-10-15
DE60201254T2 (en) 2005-09-29
WO2002055599A2 (en) 2002-07-18
JP2004522832A (en) 2004-07-29
EP1349891A2 (en) 2003-10-08
US20020132920A1 (en) 2002-09-19
EP1349891B1 (en) 2004-09-15
DE60201254D1 (en) 2004-10-21

Similar Documents

Publication Publication Date Title
US6462132B2 (en) Thermoplastic elastomer composition and molded articles made thereof
US5843577A (en) Thermoplastic elastomers having improved surface properties
US4871810A (en) Composition comprising melt blended product of thermoplastic resin and two ethylene copolymers containing coreactive groups
EP2591054B1 (en) Thermoplastic composition, method of producing the same, and articles made therefrom
KR100353192B1 (en) Soft thermoplastic elastomers having improved resistance to oil swell and compression set
KR101500779B1 (en) Crosslinkable blends of polyolefin elastomers and silane copolymers for increased flexibility cable insulation
WO2007023932A1 (en) Thermoplastic elastomer composition and composite molded article manufactured from the same
EP1672046B1 (en) Thermoplastic elastomers having improved adhesive properties
MY119696A (en) Flame retardant polycarbonate resin composition having an improved melt fluidity.
EP2233523B1 (en) Resin composition and molded article using the same
AU598808B2 (en) Thermoplastic elastomer composition
AU644398B2 (en) Imidized segmented copolymers
US4373063A (en) Elastomeric composition
JPH0579700B2 (en)
EP0341268B1 (en) Flexible thermoplastic composition
KR102573484B1 (en) Polyolefine resin composition, polyolefine master batch, process of polyolefine master batch and article using thereof
JP3043618B2 (en) Reinforced polyarylene sulfide resin composition and molded article
JP3908152B2 (en) Composite molded body
KR100345786B1 (en) Polypropylene resin composition
JP3480012B2 (en) Thermoplastic elastomer composition
KR19990060955A (en) Polypropylene Resin Composition with Excellent Paintability
CA2089517A1 (en) Processing aid for polar polymers
JP2002069202A (en) Method for manufacturing olefinic thermoplastic elastomer composition
JP2007216524A (en) Multilayer molding
JP2001342308A (en) Thermoplastic elastomer and its raw material and use

Legal Events

Date Code Title Description
AS Assignment

Owner name: DSM N.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WILLEMS, EDWIN;SADEGHI, MOHAMMAD REZA;REEL/FRAME:011758/0403;SIGNING DATES FROM 20010330 TO 20010405

AS Assignment

Owner name: DSM IP ASSETS B.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DSM N.V.;REEL/FRAME:014863/0133

Effective date: 20031208

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20141008